CN115397553A - Integrated stabilizer in deisobutanizer for isomerization of hydrocarbons and product separation - Google Patents

Integrated stabilizer in deisobutanizer for isomerization of hydrocarbons and product separation Download PDF

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Publication number
CN115397553A
CN115397553A CN202180027860.2A CN202180027860A CN115397553A CN 115397553 A CN115397553 A CN 115397553A CN 202180027860 A CN202180027860 A CN 202180027860A CN 115397553 A CN115397553 A CN 115397553A
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stream
stabilizer
isomerization
deisobutanizer
column
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CN202180027860.2A
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Inventor
M·A·苏普鲁诺夫
O·V·吉亚佐夫
D·N·沙鲁普金
A·A·卡尔马诺夫斯基
N·V·利特维内科
S·Y·杰维亚特科夫
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Kellogg Brown and Root LLC
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Kellogg Brown and Root LLC
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/20—Use of additives, e.g. for stabilisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/245—Stationary reactors without moving elements inside placed in series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
    • B01D3/322—Reboiler specifications
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2702—Catalytic processes not covered by C07C5/2732 - C07C5/31; Catalytic processes covered by both C07C5/2732 and C07C5/277 simultaneously
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/005—Processes comprising at least two steps in series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G5/00—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas
    • C10G5/06—Recovery of liquid hydrocarbon mixtures from gases, e.g. natural gas by cooling or compressing
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G7/00—Distillation of hydrocarbon oils
    • C10G7/02—Stabilising gasoline by removing gases by fractioning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/0004—Processes in series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00101—Reflux columns
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Abstract

An isomerization process includes a deisobutanizer receiving a feed comprising n-butane. The deisobutanizer delivers a portion of its bottoms to the reboiler, another portion is sent to the isomerization reactor along with hydrogen, and the reactor effluent is returned to the column. A stabilizer is integrated with the column, the overhead stream is used as reflux and the bottoms contains an isobutane rich stream, which is the isobutane product stream. The overhead effluent is sent to a separator which separates hydrocarbons from the effluent, wherein the hydrocarbons are sent to a deisobutanizer and the effluent is recycled to a stabilizer, wherein the stabilizer separates the reactor effluent into a product stream comprising an isobutane product stream, an n-butane product stream and a lighter hydrocarbon product stream.

Description

Integrated stabilizer in deisobutanizer for isomerization of hydrocarbons and product separation
Technical Field
This invention relates to the isomerization of hydrocarbons and fractionation of product effluent streams for the efficient separation of isoparaffins from feedstocks, and more particularly to such an isomerization process that includes an integrated stabilizer in the fractionation section.
Background
About 90% of the total butane consumption in the united states is in gasoline manufacture, where n-butane is used directly as a blend component and isobutane is used to make high octane alkylate or to make isobutylene for making methyl tertiary butyl ether. Chemical usage accounts for another 6-8% of the total butane. Due to the recent increase in demand for high octane gasoline, and the federally mandated reduction in gasoline vapor pressure, there is a need for a process that can efficiently convert normal butane to isobutane to ultimately increase the production of high octane blending components.
The deisobutanizer is typically operated at high reflux ratios because the boiling points of n-butane and isobutane are relatively close and a relatively pure isobutane product is desired. Thus, the heat duty of the deisobutanizer is a significant component of the operating costs of the butane isomerization process, and becomes increasingly important as higher purity isobutane product streams are sought. Accordingly, improved n-butane isomerization processes with improved capital and operating costs are sought.
The object of the present invention is a process and apparatus for the isomerization and fractionation of hydrocarbons with reduced reflux requirements and reboiler duty by means of a stabilizer integrated with a deisobutanizer.
SUMMARY
The isomerization system includes a deisobutanizer that receives a feed comprising n-butane. The deisobutanizer delivers a portion of its bottoms to the reboiler, another portion is sent to the isomerization reactor along with hydrogen, and the reactor effluent is returned to the column. A stabilizer is integrated with the column, the stabilizer overhead stream is used as reflux and the bottoms contains an isobutane rich stream, which is an isobutane product stream.
Brief Description of Drawings
Figure 1-general scheme of isobutane plant with stabilizer section; isomerizing normal butane to isobutane through a stabilizer integrated with a deisobutanizer;
FIG. 2-stabilizer section in the bottom of deisobutanizer; isomerizing normal butane to isobutane through a stabilizer integrated at the bottom of the deisobutanizer;
FIG. 3-general scheme of an isomerization unit with a stabilizer section; hydrocarbons, i.e., n-butane, n-pentane, n-hexane, n-heptane, are isomerized to isomers and heavy isomers by stabilizers integrated with the catalytic distillation column.
Detailed description of the invention
The isomerization system includes a deisobutanizer that receives a feed comprising n-butane. The deisobutanizer delivers a portion of its bottoms to the reboiler, another portion is sent to the isomerization reactor along with hydrogen, and the reactor effluent is returned to the column. A stabilizer is integrated with the column, the stabilizer overhead stream is used as reflux and the bottoms contains an isobutane rich stream, which is the isobutane product stream.
A process and apparatus for the isomerization of hydrocarbons and fractionation of a product effluent stream. Traditionally, stabilizer columns have been used for isomerization of hydrocarbons. The present invention can provide an isomerization process with lower capital costs and lower utility costs due to the integration of the stabilizer section into the rectification or reactive-rectification column. The reduction of reflux requirement of the distillation column and the reduction of reboiler duty is an effect of the present invention due to heat exchange between the stabilizer and the distillation section. Exemplary embodiments are provided below.
More specifically, as shown in FIG. 1, n-C4 isomerization; the stabilizer section is integrated into the top of the deisobutanizer. An exemplary embodiment can be a process for isomerizing a feed stream comprising n-butane. A feed stream comprising n-butane is sent to a deisobutanizer. The deisobutanizer delivers a portion of its bottoms to a reboiler, another portion from its bottoms, or from trays above the bottoms, is sent to the isomerization reactor together after mixing with hydrogen, and the reactor effluent is returned to the column. The overhead stream of the deisobutanizer is partly used as reflux and partly sent to a stable section integrated into the top of the deisobutanizer. C1-C3 hydrocarbons are removed in this portion and the bottoms product contains at least 93 wt% isobutane. This scheme has reduced the specific overall reflux requirements and reboiler duty compared to the conventional scheme in which the reactor effluent is first sent to a stabilizer column.
Another embodiment of the present invention is shown in fig. 2, n-C4 isomerization; the stabilizer section is integrated into the bottom of the deisobutanizer. Another exemplary embodiment can be a process for n-butane isomerization. The stabilizer section is integrated into the bottom section of the deisobutanizer. A feed stream comprising n-butane is sent to a deisobutanizer. The deisobutanizer delivers a portion of its bottoms to the reboiler, and another portion from its bottoms, or from trays above the bottoms, is sent to the isomerization reactor after mixing with hydrogen. The output stream from the reactor is sent to a stabilizer section where the C1-C3 hydrocarbons are removed. The bottoms stream from the stabilizer section is partially reboiled and partially sent to the deisobutanizer. Commercial iC4 product was taken from the overhead stream of the deisobutanizer. The heat integration between the stabilizer section and the bottom section of the deisobutanizer allows reducing the reboiler duty on the deisobutanizer.
Another embodiment of the present invention is shown in fig. 3, an isomerization technology with an integrated stabilizer section. Another exemplary embodiment is a process for isomerizing a C5 to C6 and/or C6 to C7 fraction. The method includes providing a hydrocarbon stream to a reaction-rectification column. The top product from the high-pressure separator is returned to the column as reflux, and the other part is sent to the stabilization section integrated into the top of the reaction-rectification column. The C1-C3 hydrocarbons are removed in this section and the bottoms product, which contains mainly branched C5+ hydrocarbons, is mixed with the isomerate product leaving the column. The present invention provides for reduced reflux requirements due to the heat integration of the stabilizer section and the distillation section of the column.
The catalytic distillation column receives the feed, wherein some portion of the feed descends through the catalytic distillation column to the reboiler and exits the column as a heavy isomer. The light portion of the feed is passed upward through a catalytic distillation column. A stabiliser is integrated with the column, the overhead stream is used as reflux after separation of lighter hydrocarbons by a low pressure separator, and the stabiliser bottoms contains an isomerate-rich product stream, a portion of which is recycled to the stabiliser after reboiling by a reboiler. The overhead is sent to a high pressure separator that separates the hydrocarbons from the effluent hydrogen, where the hydrocarbons are sent to a stabilizer in the column that is integrated with the top of the catalytic distillation column; and the effluent hydrogen is recycled to the column through a compressor and a dryer. The column contains a side draw product that is an isomer. The stream rich in isomers is taken from a point selected from the side draw of the catalytic distillation column and/or the bottom part of the stabiliser. The side draw isomerate-rich stream is a vapor, a liquid, or a combination thereof.
The stabilizer includes an overhead cooler configured to condense vapor from the column and the stabilizer. The reflux stream from the top condenser was fed to the top tray of the stabilizer.
It will be understood that the systems and methods described herein are not limited to any particular temperature range, pressure range, flow rate, stream composition, etc. It is contemplated that the systems and methods described herein may be modified by one of ordinary skill in the art to accommodate various reactor effluent compositions and other necessary conditions and parameters.
It will also be appreciated that the systems and methods described herein will have numerous technical and commercial advantages. Technical advantages include, but are not necessarily limited to:
● The fractionation efficiency is improved;
● The facility requirement is reduced;
● The overall energy requirement is reduced;
● The reflux requirement is reduced;
● The reboiler duty is reduced; and
● Isobutane loss in the system is reduced.
Commercial advantages include, but are not necessarily limited to:
● Capital requirements are reduced by 20-30% compared to conventional column schemes;
● Improved economics of fractionation;
● Less layout space (equipment footprint) requirements;
● The advantage of factory upgrade/debottlenecking;
● The value of the product is improved comprehensively; and
● The replacement of existing assets to improve the overall economics of the plant.
In the foregoing specification, the invention has been described with reference to specific embodiments thereof. The description is to be regarded as illustrative instead of limiting. For example, equipment, columns, stabilizers, processes, reactants, normal paraffins, isoparaffins, products, isomers, and operating conditions falling within the claimed or disclosed parameters, but not specifically stated or tried in a particular example, are intended to be within the scope of this invention.
The invention may be practiced in the absence of any element which is not disclosed. In addition, the invention can suitably comprise, consist of, or consist essentially of the disclosed elements. The isomerization system includes a deisobutanizer or catalytic distillation tower that receives a feed comprising n-butane. The deisobutanizer delivers a portion of its bottoms to the reboiler, another portion is sent to the isomerization reactor along with hydrogen, and the reactor effluent is returned to the column. A stabilizer is integrated with the column, the top stream of the stabilizer is used as reflux, the lighter hydrocarbons are C1-C3 hydrocarbons, and the bottoms contains an isobutane-rich stream, which is the isobutane product stream.
The words "comprising" and "including" as used throughout the claims are to be construed to mean "including but not limited to" and "including but not limited to", respectively.
As used herein, the term "substantially" shall mean "largely but not completely specified".
As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
As used herein, the term "about" in reference to a given parameter includes the stated value and has the meaning dictated by the context (e.g., it includes the degree of error associated with measurement of the given parameter).
As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

Claims (16)

1. Isomerization of normal paraffins which comprises:
the deisobutanizer receives a feed comprising normal paraffins that comprise the feedstock, which delivers a portion to the reboiler;
the isomerization reactor receives another portion from the deisobutanizer bottoms or from trays above the bottoms, mixed with hydrogen, and the reactor effluent is returned to the column;
a stabilizer is integrated with the column, the overhead stream is used as reflux and the bottoms contains an isomerate-rich stream, which is an isomerate product stream;
a separator receiving an overhead stream that separates the hydrocarbons into at least two streams, wherein a first stream is sent to the deisobutanizer as its reflux and the remaining stream is sent to the stabilizer;
wherein the stabilizer separates the reactor effluent into a product stream comprising:
a isomerate product stream, and
a lighter hydrocarbon product stream.
2. The isomerization of normal paraffins in accordance with claim 1, wherein at least a portion of the isomerate product stream is recycled to the stabilizer in a recycle stream.
3. The isomerization of normal paraffins in accordance with claim 1 wherein the stabilizer separates the isomerate effluent into branched C4+ hydrocarbons and a lighter hydrocarbon product stream and hydrogen.
4. The isomerization of normal paraffins of claim 1 further comprising an intermediate reboiler in the bottom section of the reboiler and wherein the isomerate product stream is the heating medium in the intermediate reboiler.
5. A process for the isomerization of n-butane comprising:
the n-butane rich fraction is the feed to a deisobutanizer including a stabilizer;
the reactor effluent is the feed to the deisobutanizer including a stabilizer;
the deisobutanizer delivers a portion of its bottoms to the reboiler, another portion is sent to the isomerization reactor after mixing with hydrogen, and the reactor effluent is returned to the stabilizer;
the stabilizer is integrated with the column of the deisobutanizer;
the stabilizer comprises tower top light hydrocarbon and hydrogen, wherein the tower top light hydrocarbon is C1-C3 hydrocarbon;
the column has an overhead product extracted from the column and/or the stabilizer that is an isomerate stream that is an isobutane product stream.
6. The process of claim 5, wherein the overhead isobutane-rich stream is a recycle stream to the deisobutanizer.
7. The process of claim 5, further comprising an intermediate reboiler in the bottom portion of the deisobutanizer.
8. A process for the isomerization of normal paraffins which comprises:
a catalytic distillation column receiving a feed comprising normal paraffins, the catalytic distillation column delivering a portion of its bottoms to a reboiler, another portion being heavy isomers;
a stabiliser is integrated with the column, the overhead stream is used as reflux after separation of lighter hydrocarbons by a low pressure separator, the stabiliser bottoms contains an isomerate-rich product stream, and a portion is recycled to the stabiliser after reboiling by a reboiler;
the overhead is sent to a high pressure separator that separates the hydrocarbons from the effluent hydrogen, where the hydrocarbons are sent to a stabilizer in the column that is integrated with the top of the deisobutanizer;
the column has a side draw product that is an isomer;
wherein the stabilizer separates the reactor effluent into a product stream comprising:
an isomerate product stream, and
a light hydrocarbon stream.
9. The isomerization process of claim 8, wherein the feed is a C5-C6, C6-C7, C5-C7 fraction.
10. The isomerization process of claim 8 wherein the lighter hydrocarbon product stream comprises C1-C3 hydrocarbons.
11. The isomerization process of claim 8 wherein the isomerate product stream is branched C4+ hydrocarbons.
12. The isomerization process of claim 8 further comprising an intermediate reboiler in the bottom portion of the reboiler, and wherein the isomerate product stream is the heating medium in the intermediate reboiler.
13. The isomerization process of claim 8 wherein the stabilizer is at or near the top of the column or near the bottom of the column.
14. The isomerization process of claim 8 wherein the isomerate-rich stream is taken from a point selected from the side draw of the catalytic distillation column and/or the bottom portion of the stabilizer.
15. The isomerization process of claim 8 wherein the side draw for the isomerate-rich stream is selected from vapor, liquid or combinations thereof.
16. The isomerization process of claim 8 wherein the stream enriched in isomers is a branched C4+ hydrocarbon.
CN202180027860.2A 2020-04-16 2021-04-13 Integrated stabilizer in deisobutanizer for isomerization of hydrocarbons and product separation Pending CN115397553A (en)

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